Sonogashira Hagihara Research Articles

Utilizing Hairy Hollow Conjugated Microporous Polymers and Native Enzymes for Precise Aerobic Photocatalysis Under Near‐Infrared Wavelengths

AbstractUtilizing photoregenerated cofactors in conjunction with enzymes in a sequential manner presents an effective approach for the synthesis of targeted compounds in gentle reaction conditions. Nevertheless, the integration of enzymes and photocatalysts has faced challenges due to the swift breakdown of biomaterials caused by high‐energy or blue lights and photoinduced reactive oxygen species, leading to the denaturation and deactivation of enzymatic materials. This study details the deliberate development and production of hairy hollow conjugated microporous polymers (S‐hPrTZ‐P HCMPs), achieved via Sonogashira–Hagihara coupling on SiO2 templates, followed by sulfonation, polymer grafting and ultimately eliminating the SiO2 cores. This technique leverages the distinctive characteristics of low‐energy near‐infrared light, such as its superior penetration ability, to effectively regenerate the enzymatic cofactor NAD+ from NADH. It can accomplish this feat even when faced with synthetic or biological barriers that are impermeable to visible light. Simultaneously, photogenerated reactive oxygen species are captured and neutralized by the hydrophilic polymer brushes, safeguarding the integrity of the enzymatic material. The adaptability of S‐hPrTZ‐P with photocatalytic properties is showcased alongside glucose 1‐dehydrogenase and glycerol dehydrogenase. This structure and morphology‐controlled strategy offers a promising pathway for various enzymatic photobiocatalysis employing stable, efficient, and reusable hairy HCMPs.

Synthesis of conjugated microporous polymers rich in sulfonic acid groups for the highly efficient adsorption of Cs+

Conjugated microporous polymers (CMPs) with extended π-conjugated systems and permanent microporous scaffolders have broad application prospects in the treatment of radionuclides in nuclear wastewater. Herein, the Sonogashira–Hagihara coupling process was employed to generate three CMPs, called CMP1–3. CMP1S–3S with different degrees of sulfonation were produced and employed for Cs+ ion adsorption by adjusting the sulfonation time using chlorosulfonic acid as the sulfonating agent. This is the first attempt to apply CMPs containing sulfonic acid groups to Cs+ ion adsorption, which show excellent adsorption properties. CMP1S-48 with the highest surface sulfonic acid group density exhibited the fastest adsorption rate, and it reached adsorption equilibrium on Cs+ ion in an aqueous solution under 1 min. The adsorption process corresponded to the Freundlich isotherm model of multilayer adsorption, with an adsorption capacity of up to 288.1 mg g−1. Compare with CMP2S-48 and CMP3S-48, CMP1S-48 with more sulfonic acid groups shows the highest adsorption capacity. Moreover, the selectivity of CMP1S-48 adsorbing Cs+ ion was exceeded high. Notably, the adsorption mechanism of Cs+ ion by CMP1S–3S involved ion exchange with H+ in the sulfonic acid groups, as well as its complexation and electrostatic attraction with the sulfonic acid groups. This work opens up a new way for CMPs rich in sulfonic acid groups to treat Cs+ ion-contaminated water sources.

Bipyridine-containing π-conjugated polymers bearing optically active amide groups: mechanistic aspects of formation of chiral higher-order structures

A helically foldable bipyridine-containing poly(phenyleneethynylene) was synthesized by the Sonogashira–Hagihara coupling polymerization of N-(3,5-diethynylbenzoyl)-l-alanine dodecyl ester with 4,4′-dibromo-2,2′-bipyridine.

Synthesis of geometry-controlled platinum-containing polymers bearing optically active bidentate phosphine ligands

Pt-diyne polymers were synthesized by dehydrochlorination coupling polymerization of a cis-PtCl2 complex with 1,4-diethynylbenzene, and Sonogashira–Hagihara coupling polymerization of a cis-Pt diethynyl complex with 1,3- and 1,4-diiodobenzenes.

Direct synthesis of N, S co‐doped graphynes via copolymerization strategy for electrocatalytic application

AbstractGraphynes (GYs) are a novel set of carbon allotropes with high potential as future catalytic electrodes for oxygen reduction reactions because of their unique physical and chemical properties. In recent years, a number of heteroatom‐doped graphdiyne (GDYs) based electrocatalysts have been developed. However, the development of GYs has made slow progress due to their limited synthetic strategies. Here, the first case of nitrogen and sulfur co‐doped graphynes (NS‐GYs) synthesized through the copolymerization between hydrogen‐deficient heterocyclic aromatic monomers via the Sonogashira–Hagihara cross‐coupling reaction is reported. The NS‐GYs exhibit abundant porosity after heat treatment with large specific area and high heteroatom content for use as potential electrocatalysts. In addition, NS‐GY‐3‐800 with the best electrocatalytic performance shows excellent power density and stability in Zn‐air batteries.

Rational design and synthesis of bifunctional Dibenzo[g,p]chrysene-based conjugated microporous polymers for energy storage and visible light-driven photocatalytic hydrogen evolution

The importance of conjugated microporous polymers (CMPs) as active components in photocatalytic hydrogen evolution is growing due to its intense ultraviolet–visible (UV–vis) absorption, potent fluorescence, and high carrier transport capacity, dibenzo[g,p]chrysene shows notable photophysical and electrical features. This is because CMPs have stiff molecular structures with large π-conjugation. In this section, we describe our approach and syntheses of three types of polymers for the first time to determine the reactivity of dibenzo[g,p]chrysene (TBN)-based CMPs for photocatalytic H2 evolution and energy storage applications. Three TBN-based CMPs, TBN-TBN (D-D), TBN-TBN-TPA (A-D), and TBN-TBN-BT (D-A), were synthesized via Sonogashira–Hagihara coupling. TBN-CMP materials were used as working electrodes for energy storage applications. The TBN-TBN-BT CMP demonstrated excellent capacity retention (98.2%) over 2000 cycles and high capacitor (130 F g−1) at 0.5 A g−1, in accordance with electrochemical performance. Furthermore, the hydrogen evolution rate (HER) results are in the following order 8452, 9800, and 3060 μmol g−1h−1 for TBN-TBN, TBN-TBN-TPA, and TBN-TBN-BT CMPs, respectively. These findings suggest that using TBN as an acceptor increases the number of active sites for proton reduction, thereby boosting the rate of H2 evolution.

A hexaazatriphenylene‐based porous organic polymer for high performance supercapacitor

AbstractPorous organic polymers (POPs) with high physiochemical stability and pseudocapacitive activity are crucial for supercapacitors with high specific capacitance and long cycle life. We report herein a hexaazatrinaphthylene‐based POP (HPOP‐1) for high‐performance supercapacitor by introducing redox‐active hexaazatrinaphthylene (HATN) moiety through Sonogashira–Hagihara coupling reaction. HATN moiety can undergo a proton‐induced electron transfer redox reaction, which endows HPOP‐1 with high pseudocapacitive activity. As electrode materials for supercapacitor application, HPOP‐1 exhibits high specific capacitance (667 F g−1 at 0.5 A g−1) and long‐term cyclic stability (90% capacitance retention after 10,000 cycles at 5 A g−1) in a three‐electrode system with 1 M H2SO4 as the electrolyte. In addition, HPOP‐1 also exhibits a specific capacitance of 376 F g−1 at 0.5 A g−1 in 1 M KOH electrolyte. An asymmetric supercapacitor was further fabricated with HPOP‐1 as negative electrode and rGO as positive electrode, respectively. The device delivers a specific capacitance of 63 F g−1 at 0.5 A g−1 and a rate performance of 37 F g−1 at 5 A g−1. Our work provides a facile approach for the design and preparation of pseudocapacitive POPs with high specific capacitance and long cycle life.

Removal of PM and oil mist from automobile exhaust by a “hamburger” structured conjugated microporous polymers membrane

The purification treatment of automobile exhaust has attracted great attention because of the severe harm of automobile exhaust to the global environment and human health. Herein, inspired by capillarity, we adopted a very simple face-to-face constrained growth method to prepare a conjugated microporous polymers membrane (C-CMPs-M) with a “Hamburger” structure through Sonogashira-Hagihara (S-H) coupling reaction for purification and filtration of gaseous, solid and liquid pollutants in automobile exhaust. Thanks to such a special structure, the C-CMPs-M−1 membrane shows an extremely high efficiency of capture and interception of PM2.5 and PM10 (greater than99.5 %) and PM0.3 (greater than95%) in the exhaust gas obtained at different engine speeds. Unlike those hydrophilic filtration materials which suffer the drawback of less tolerance in high humidity conditions, the unique superhydrophobic chemistry of the CMPs membrane makes it possible to efficiently intercept PM under high humidity conditions, and the filtration efficiency basically remains unchanged within 10 h. More interestingly, the super lipophilicity of the membrane endows it excellent oil absorption performance, e.g., high absorption of 907.61 % of its own weight for engine oil was detected and consequently good oil retention performance was also obtained. It also has a strong absorption performance for the unburned oil mist ejected from the exhaust. Based on its ideal porous structure, high interception efficiency, and good physicochemical stability at high humidity and high temperatures conditions, therefore, our C-CMPs-M−1 shows great potential in automobile exhaust purification applications.

In Situ Modification of Multi-Walled Carbon Nanotubes with Polythiophene-Based Conjugated Polymer for Information Storage.

One-dimensional multi-walled carbon nanotubes (MWNTs) have unique electrical properties, but they are not solution-processable, which severely limits their applications in microelectronic devices. Therefore, it is of great significance to improve the solubility of MWNTs and endow them with new functions by chemical modification. In this work, MWNTs were in situ functionalized with poly[(1,4-diethynyl-benzene)-alt-(3-hexylthiophene)] (PDHT) via Sonogashira-Hagihara polymerization. The obtained material PDHT-g-MWNTs was soluble in conventional organic solvents. By sandwiching a PDHT-g-MWNTs film between Al and ITO electrodes, the fabricated Al/PDHT-g-MWNTs/ITO electronic device exhibited nonvolatile rewritable memory behavior, with highly symmetrical turn-on/off voltages, a retention time of over 104 s, and durability for 200 switching cycles. These findings provide important insights into the development of carbon nanotube-based materials for information storage.

Solid state chemical transformation provides a fully benzoxazine-linked porous organic polymer displaying enhanced CO2 capture and supercapacitor performance

We synthesized a fully benzoxazine (BZ)-linked POP comprising TPA and DHPT units through Sonogashira–Hagihara coupling and ring opening polymerization for CO2 capture and energy storage.

Gold and palladium supported on an ionic liquid modified Fe-based metal-organic framework (MOF) as highly efficient catalysts for the reduction of nitrophenols, dyes and Sonogashira-Hagihara reactions.

Two supported noble metal species, gold and palladium anchored on an ionic liquid-modified Fe-based metal-organic framework (MOF), were successfully synthesized and characterized by FT-IR, XRD, TEM, XPS, SEM, EDX, and elemental mapping. The ionic liquid post-modified MOF was used for anchoring Au or Pd at ppm levels, and the resulting materials were employed as catalysts in the reduction of nitrophenol isomers, dyes, and Sonogashira-Hagihara reactions. Using the Au@Fe-MOF-IL catalyst, reduction of nitrophenol isomers, as well as the reductive degradation of dyes, e.g., methylene blue (MB), methyl orange (MO), and methyl red (MR) were performed efficiently in water. On the other hand, Pd@Fe-MOF-IL was used as an effective catalyst in the Sonogashira-Hagihara coupling reaction of aryl iodides and bromides using very low amounts of Pd. These catalysts were recycled and reused for several runs without deteriorating remarkably in catalytic performance.

A hollow viologen-based porous organic polymer for the catalytic cycloaddition of CO2

Viologen-based porous organic polymers with a hollow structure were synthesizedviaa Sonogashira–Hagihara cross-coupling reaction. They showed excellent catalytic performance for the carbon-dioxide cycloaddition reaction.

Polypyrrole-coated conjugated microporous polymers/expanded graphene carbon aerogels based phase change materials composites for efficient energy conversion and storage

Phase change materials (PCMs) composites are of great importance for a wide range of applications in energy conversion and storage, waste heat recovery and utilization, thermal energy management in building, electronic devices cooling and heat insulation, etc. Herein, a novel strategy for the fabrication of PCM composites for solar/electro energy conversion and storage is reported. The polypyrrole (PPy) coated conjugated microporous polymers/expanded graphene (EG) carbon aerogels/HDA (PCMPECAs/HDA) composites were firstly obtained via Sonogashira–Hagihara cross-coupling reaction followed by a carbonization treatment, PPy coating and finally 1-Hexadecylamine (HDA) impregnation. The introduction of EG and PPy was to improve the porosity, thermal conductivity and photothermal performance. The resultant PCMPECAs/HDA composites exhibited excellent comprehensive performances, including relatively high thermal conductivity of up to 234.0% that of HDA, high energy storage density up to 205.10 kJ/kg, excellent shape and thermal stability and a remarkable photothermal conversion and storage efficiency of up to 93.5%, respectively. And after 300 times thermal and cooling cycles, the latent heat of PCMPECAs/HDA still remains up to 150.20 kJ/kg. Besides, the resultant composites also manifest excellent electro-thermal effect at low voltage. Due to the aforementioned advantages, PCMPECAs/HDA composites possess great potential applications in solar/electric energy conversion and storage. • Conjugated microporous polymer carbon aerogels composites are first reported. • The latent heat of PCMPECAs/HDA composites were tested up to 205.10 kJ/kg • The resultant composites show an ultrahigh photothermal conversion efficiency (93.5%). • The shape-stable composite has a phase change enthalpy of 150.20 kJ kg -1 after 300 cycles. • The resultant composites presented an excellent electro-thermal effect at low voltage.

Fluorine-functionalized conjugated microporous polymer as adsorbents for solid-phase extraction of nine perfluorinated alkyl substances

Perfluorinated alkyl substances (PFASs) are persistent, toxic, ubiquitously distributed, and bioaccumulated substances, which have attracted increasing concern. To investigate the environmental effects of PFASs, there is a need to develop a sensitive, rapid, and efficient method for detecting trace level PFASs. In this study, a conjugated microporous polymer (CMP) with loading of fluorine, fabricated by Sonogashira–Hagihara cross-coupling, was exploited as a solid-phase extraction (SPE) adsorbent. The prepared fluorine-functionalized CMP (FCMP), which showed a large surface area of 1089 m2·g−1, high porosity, and good chemical stability, was used to extract PFASs from water samples. The adsorption mechanism was investigated using a sorption isotherm model, and the main interactions were fluorous and hydrophobic affinity. The FCMP-based SPE combined with high-performance liquid chromatography-tandem mass spectrometry achieved low limits of detection (0.19–0.97 ng·L−1), wide linear range (2–1600 ng·L−1), and good reproducibility (3.4%–12.9%) under the optimal conditions. Furthermore, the approach was utilized for the analysis of three water samples (snow, river water, and irrigation water) to evaluate its reliability, and satisfactory recovery (70.5%–127.5%) was obtained. Thus, FCMP was feasible SPE adsorbents for the selective extraction of PFASs.

Eucalyptol, an All-Purpose Product

Eucalyptus plants have attracted the attention of researchers and environmentalists worldwide because they are a rapidly growing source of wood and a source of oil used for multiple purposes. The main and the most important oil component is 1,8-cineole (eucalyptol: 60–85%). This review summarizes the literature reported to date involving the use of 1,8-cineole for the treatment of disorders. Additionally, we describe our efforts in the use of eucalyptol as a solvent for the synthesis of O,S,N-heterocycles. Solvents used in chemistry are a fundamental element of the environmental performance of processes in corporate and academic laboratories. Their influence on costs, safety and health cannot be neglected. Green solvents such as bio-based systems hold considerable additional promise to reduce the environmental impact of organic chemistry. The first section outlines the process leading to our discovery of an unprecedented solvent and its validation in the first coupling reactions. This section continues with the description of its properties and characteristics and its reuse as reported in the various studies conducted. The second section highlights the use of eucalyptol in a series of coupling reactions (i.e., Suzuki–Miyaura, Sonogashira–Hagihara, Buchwald–Hartwig, Migita–Kosugi–Stille, Hiyama and cyanation) that form O,S,N-heterocycles. We describe the optimization process applied to reach the ideal conditions. We also show that eucalyptol can be a good alternative to build heterocycles that contain oxygen, sulfur and nitrogen. These studies allowed us to demonstrate the viability and potential that bio solvents can have in synthesis laboratories.

A Carbazole-Functionalized Porous Aromatic Framework for Enhancing Volatile Iodine Capture via Lewis Electron Pairing.

Nitrogen-rich porous networks with additional polarity and basicity may serve as effective adsorbents for the Lewis electron pairing of iodine molecules. Herein a carbazole-functionalized porous aromatic framework (PAF) was synthesized through a Sonogashira–Hagihara cross-coupling polymerization of 1,3,5-triethynylbenzene and 2,7-dibromocarbazole building monomers. The resulting solid with a high nitrogen content incorporated the Lewis electron pairing effect into a π-conjugated nano-cavity, leading to an ultrahigh binding capability for iodine molecules. The iodine uptake per specific surface area was ~8 mg m−2 which achieved the highest level among all reported I2 adsorbents, surpassing that of the pure biphenyl-based PAF sample by ca. 30 times. Our study illustrated a new possibility for introducing electron-rich building units into the design and synthesis of porous adsorbents for effective capture and removal of volatile iodine from nuclear waste and leakage.

Metal scavenging and catalysis by periodic mesoporous organosilicas with 2,2′‐bipyridine metal chelating ligands

AbstractA periodic mesoporous organosilica containing 2,2′‐bipyridine (BPy‐PMO) was assessed as a metal scavenger and heterogeneous catalyst. The functionalized PMO was synthesized based on a modified version of a previously reported procedure and showed a large surface area with crystal‐like pore walls and uniformly small particles. The small BPy‐PMOs (s‐BPy‐PMOs) exhibited efficient adsorption and removal of palladium (Pd2+) and copper (Cu2+) ions from THF solutions, as confirmed by inductively coupled plasma and UV/vis spectroscopy analyses. The removal efficiencies for Pd and Cu were determined to be 99.9% and 97.5%, respectively. This material was also used to scavenge residual Pd and Cu from reagent solutions following Sonogashira–Hagihara coupling, during which C–C bonds are generated based on catalysis by these metals. Moreover, Pd2+supportings‐BPy‐PMO was found to act as an efficient heterogeneous catalyst for the Sonogashira–Hagihara coupling reaction and could be easily separated from the reaction solution by simple filtration and reused.

Thiol/methylthio-functionalized porous aromatic frameworks for simultaneous capture of aromatic pollutants and Hg(II) from water

Simultaneously capturing organic pollutants and heavy metal can greatly reduce the water remediation time and cost, however it is still a great challenge presently. Herein, two novel thiol/methylthio–functionalized porous aromatic frameworks were synthesized as sorbents via the Sonogashira–Hagihara reaction of 1,3,5–triethynylbenzene and 1,3,5–tris(4–bromophenyl) benzene, the subsequent chloromethylation of the phenyl rings, and the final nucleophile substitution of –Cl groups by NaSH/NaSMe. These two sorbents were characterized by FT–IR spectra, energy dispersive X-ray spectra, scanning electron microscope, nitrogen adsorption analysis, thermo–gravimetric analysis, and elemental analyses. Adsorption experiments displayed that new sorbents had high uptake abilities and fast adsorption kinetics for aromatic pollutants and mercury (II) (Hg(II)). The maximum adsorption capacity (Qmax) of toluene and m–xylene on both new sorbents were 531.9–571.4 mg/g with the kinetic binding rate constants (kobs) of 0.00276–0.02422 g/mg/min, and the Qmax values of Hg(II) were 148.1–180.3 mg/g with kobs of 0.00592–0.01573 g/mg/min. Moreover, new sorbents indicated high simultaneous uptake abilities for these pollutants with good reusability, and finally they were successfully applied to the simultaneous remediation of these pollutants in two simulated sewages with high and low concentration, indicating their great practical application potential in wastewater remediation.

Solid-State Chemical Transformations to Enhance Gas Capture in Benzoxazine-Linked Conjugated Microporous Polymers

We describe the first examples of benzoxazine (BZ)-linked tetraphenylethylene (TPE)- and pyrene (Py)-containing conjugated microporous organic polymers (CMPs)—TPE-TPE-BZ and Py-TPE-BZ, respectively—having high surface areas and pore volumes, prepared through multistep syntheses (Schiff base, reduction, Mannich, and Sonogashira–Hagihara coupling), and their solid-state transformations through ring-opening polymerizations (ROPs) to give BZ linkages have never been reported previously. The chemical structures and, particularly, the presence of BZ units in the TPE-TPE-BZ and Py-TPE-BZ CMPs were confirmed through Fourier transform infrared and solid-state nuclear magnetic resonance spectroscopic analyses. The TEP-TPE-BZ CMP had a high BET specific surface area and a high total pore volume (325 m2 g–1 and 0.69 cm3 g–1, respectively). Because BZ units can undergo ROP through simple thermal treatment without the need for a curing agent or catalyst, the CMPs readily underwent one-step chemical transformations in the solid state to form new CMPs featuring phenolic OH and Mannich bridges as functional groups capable of forming strong intermolecular hydrogen bonds and/or acid/base interactions with molecules of CO2 gas to enhance the gas uptake ability.

Co3O4 nanoparticles embedded in triple-shelled graphitic carbon nitride (Co3O4/TSCN): a new sustainable and high-performance hierarchical catalyst for the Pd/Cu-free Sonogashira–Hagihara cross-coupling reaction in solvent-free conditions

Co3O4 nanoparticles embedded in triple-shelled graphitic carbon nitride (Co3O4/TSCN): a new sustainable and high-performance hierarchical catalyst for the Pd/Cu-free Sonogashira–Hagihara cross-coupling reaction in solvent-free conditions